Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility

Abstract

Embodiments are directed to a catalyst system comprising metal-ligand complexes and processes for polyolefin polymerization using the metal-ligand complex having the following structure, Formula (I), where X is selected from the group consisting of —(CH2)SiRX3.

The invention claimed is: 
     
       1. A catalyst system comprising a metal-ligand complex according to formula (I): 
       
         
           
           
               
               
           
         
       
       where:
 M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4; 
 X is selected from the group consisting of —(CH 2 )SiR X   3 , where each R X  is independently a (C 1 -C 30 )hydrocarbyl or a (C 1 -C 30 )heterohydrocarbyl and at least one of R X  is a (C 2 -C 30 )hydrocarbyl, where any two R X  or all three R X  are optionally covalently linked; 
 each Z is independently chosen from —O—, —S—, —N(R N )—, or —P(R P )—; 
 each of R 1  and R 16  is independently selected from the group consisting of —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV): 
 
       
         
           
           
               
               
           
         
          where each of R 31 -R 35 , R 41 —R 48 , and R 51 —R 59  is independently chosen from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R N )—, (R C ) 2 NC(O)—, or halogen,
 provided that at least one of R 1  or R 16  is a radical having formula (II), a radical having formula (III), or a radical having formula (IV); 
 
         each of R 2 -R 4 , R 5 -R 8 , R 9 -R 12 , and R 13 -R 15  is independently selected from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, and halogen; 
         L is (C 2 -C 40 )hydrocarbylene or (C 2 -C 40 )heterohydrocarbylene; and 
         each R C , R P , and R N  in formula (I) is independently a (C 1 -C 30 )hydrocarbyl, (C 1 -C 30 )heterohydrocarbyl, or —H. 
       
     
     
       2. The catalyst system according to  claim 1 , wherein:
 M is zirconium or hafnium; 
 each X is —(CH 2 )Si(CH 3 ) 2 (CH 2 CH 3 ); and 
 each Z is oxygen. 
 
     
     
       3. The catalyst system according to  claim 1 , wherein:
 M is zirconium or hafnium; 
 each X is —(CH 2 )Si(CH 2 CH 3 ) 3 ; and 
 each Z is oxygen. 
 
     
     
       4. The catalyst system according to  claim 1 , wherein
 M is zirconium or hafnium; 
 each X is selected from the group consisting of —(CH 2 ) Si(CH 3 )(n-Oct)R X ; and 
 each Z is oxygen. 
 
     
     
       5. The catalyst system according to  claim 1 , wherein exactly two R X  are covalently linked or exactly three R X  are covalently linked. 
     
     
       6. The catalyst system according to  claim 1 , wherein
 M is zirconium or hafnium; 
 each X is selected from the group consisting of —(CH 2 )Si(CH 3 ) 2 (n-butyl); and 
 each Z is oxygen. 
 
     
     
       7. The catalyst system according to  claim 1 , wherein
 M is zirconium or hafnium; 
 each X is —(CH 2 )Si(CH 3 ) 2 (n-hexyl); and 
 each Z is oxygen. 
 
     
     
       8. The catalyst system according to  claim 1 , wherein
 M is zirconium or hafnium; 
 each X is —(CH 2 )Si(CH 3 ) 2 (2-ethylhexyl); and 
 each Z is oxygen. 
 
     
     
       9. The catalyst system according to  claim 1 , wherein
 M is zirconium or hafnium; 
 each X is —(CH 2 )Si(CH 3 ) 2 (dodecyl); and 
 each Z is oxygen. 
 
     
     
       10. The catalyst system according to  claim 1 , wherein
 M is zirconium or hafnium; 
 each X is —CH 2 Si(CH 3 ) 2 CH 2 Si(CH 3 ) 3 ; and 
 each Z is oxygen. 
 
     
     
       11. The catalyst system according to  claim 1 , wherein the metal-ligand complex according to formula (I) has a wt % solubility ratio W/Y of at least 1.5, wherein W is the wt % solubility of the metal-ligand complex of formula (I) in methylcyclohexane (MCH) at standard temperature and pressure (STP); wherein Y is the wt % of a corresponding comparative metal-ligand complex of formula (Ia) in MCH at STP; and wherein the corresponding comparative complex has a structure according to formula (Ia): 
       
         
           
           
               
               
           
         
         in which M, each Z, each R 1 -R 16 , and L all are identical to corresponding groups of the metal-ligand complex according to formula (I). 
       
     
     
       12. A catalyst system comprising a metal-ligand complex according to formula (I): 
       
         
           
           
               
               
           
         
       
       where:
 M is zirconium or hafnium being in a formal oxidation state of +2, +3, or +4; 
 X is selected from the group consisting of —(CH 2 )Si(CH 3 )(n-Oct)R X , —(CH 2 )Si(CH 3 ) 2 (n-hexyl), —(CH 2 )Si(CH 3 ) 2 (2-ethylhexyl), —(CH 2 )Si(CH 3 ) 2 (dodecyl), and —CH 2 Si(CH 3 ) 2 CH 2 Si(CH 3 ) 3 , where R X  is a (C 1 -C 30 )hydrocarbyl or a (C 1 -C 30 )heterohydrocarbyl; 
 each Z is —O—; 
 each of R 1  and R 16  is independently selected from the group consisting of —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV): 
 
       
         
           
           
               
               
           
         
          where each R 31 -R 35 , R 41 R 48 , and R 51 -R 59  is independently chosen from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R N )—, (R C ) 2 NC(O)—, or halogen,
 provided that at least one of R 1  or R 16  is a radical having formula (II), a radical having formula (III), or a radical having formula (IV); 
 
         each of R 2 -R 4 , R 5 -R 8 , R 9 -R 12 , and R 13 -R 15  is independently selected from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, and halogen; 
         L is (C 2 -C 40 )hydrocarbylene or (C 2 -C 40 )heterohydrocarbylene; and 
         each R C , R P , and R N  in formula (I) is independently a (C 1 -C 30 )hydrocarbyl, (C 1 -C 30 )heterohydrocarbyl, or —H.